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WO2019020522A1 - Process for the co-production of methanol and ammonia - Google Patents

Process for the co-production of methanol and ammonia Download PDF

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Publication number
WO2019020522A1
WO2019020522A1 PCT/EP2018/069793 EP2018069793W WO2019020522A1 WO 2019020522 A1 WO2019020522 A1 WO 2019020522A1 EP 2018069793 W EP2018069793 W EP 2018069793W WO 2019020522 A1 WO2019020522 A1 WO 2019020522A1
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Prior art keywords
gas
hydrogen
methanol
stream
ammonia
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PCT/EP2018/069793
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French (fr)
Inventor
Pat A. Han
Original Assignee
Haldor Topsøe A/S
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Priority to NZ760487A priority Critical patent/NZ760487A/en
Priority to PL18743790.0T priority patent/PL3658493T3/en
Priority to KR1020207003908A priority patent/KR102599470B1/en
Priority to EP18743790.0A priority patent/EP3658493B1/en
Priority to AU2018308863A priority patent/AU2018308863B2/en
Priority to BR112020001511-3A priority patent/BR112020001511B1/en
Priority to CA3070745A priority patent/CA3070745A1/en
Application filed by Haldor Topsøe A/S filed Critical Haldor Topsøe A/S
Priority to CN201880045412.3A priority patent/CN110831893A/en
Priority to PE2020000124A priority patent/PE20200652A1/en
Priority to EA202090363A priority patent/EA039172B1/en
Priority to UAA202001253A priority patent/UA127220C2/en
Priority to US16/622,463 priority patent/US11053130B2/en
Publication of WO2019020522A1 publication Critical patent/WO2019020522A1/en
Priority to ZA2019/08175A priority patent/ZA201908175B/en
Priority to IL271942A priority patent/IL271942B2/en

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
    • C01C1/00—Ammonia; Compounds thereof
    • C01C1/02—Preparation, purification or separation of ammonia
    • C01C1/04—Preparation of ammonia by synthesis in the gas phase
    • C01C1/0405—Preparation of ammonia by synthesis in the gas phase from N2 and H2 in presence of a catalyst
    • C01C1/0488—Processes integrated with preparations of other compounds, e.g. methanol, urea or with processes for power generation
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/025—Preparation or purification of gas mixtures for ammonia synthesis
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
    • C01B3/382—Multi-step processes
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
    • C01C1/00—Ammonia; Compounds thereof
    • C01C1/02—Preparation, purification or separation of ammonia
    • C01C1/024—Purification
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
    • C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
    • C07C29/1516—Multisteps
    • C07C29/1518—Multisteps one step being the formation of initial mixture of carbon oxides and hydrogen for synthesis
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/02—Hydrogen or oxygen
    • C25B1/04—Hydrogen or oxygen by electrolysis of water
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B15/00—Operating or servicing cells
    • C25B15/08—Supplying or removing reactants or electrolytes; Regeneration of electrolytes
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
    • C01B2203/0211—Processes for making hydrogen or synthesis gas containing a reforming step containing a non-catalytic reforming step
    • C01B2203/0216—Processes for making hydrogen or synthesis gas containing a reforming step containing a non-catalytic reforming step containing a non-catalytic steam reforming step
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
    • C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
    • C01B2203/0244—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being an autothermal reforming step, e.g. secondary reforming processes
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0283—Processes for making hydrogen or synthesis gas containing a CO-shift step, i.e. a water gas shift step
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/046—Purification by cryogenic separation
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/06—Integration with other chemical processes
    • C01B2203/061—Methanol production
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/06—Integration with other chemical processes
    • C01B2203/068—Ammonia synthesis
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency
    • Y02P20/133—Renewable energy sources, e.g. sunlight
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

  • the present invention is directed to the co-production of methanol and ammonia. More particular, the invention is based on electrolysis of water and steam reforming of a gas- eous hydrocarbon feed stock in the preparation of a carbon oxide, hydrogen and nitrogen containing synthesis gas, which in a first process stage is subjected to methanol synthesis and in a second process stage to ammonia synthesis.
  • synthesis gas is typically prepared in so-called two step reforming process.
  • a desulfurized hydrocarbon feed stock usually natural gas
  • SMR primary steam methane reformer
  • adiabatic secondary steam reformer by partial oxidation of hydrogen and hydrocarbons and adiabatic steam reforming of residual amounts of hydrocarbons from the partial oxidation step.
  • the adiabatic second- ary reformer is operated with essentially pure oxygen for use in the partial oxidation step.
  • the essentially pure oxygen is typically supplied from an Air Separation Unit (ASU).
  • ASU Air Separation Unit
  • stand-alone SMR or stand-alone autothermal re- forming can be used to prepare the synthesis gas.
  • the product gas will comprise hydrogen, carbon monoxide, and carbon dioxide as well as other components normally including methane and steam.
  • Ammonia synthesis gas is conventionally prepared by subjecting hydrocarbon feed of natural gas or higher hydrocarbons to endothermic steam reforming reactions in a fired tubular steam reformer by contact with a steam reforming catalyst.
  • the primary reformed gas is then fed into an adiabatic secondary reformer, wherein part of hydrogen and residual amounts of hydrocarbons in the primary reformed gas are partial oxidized with oxygen enriched process air in presence of a secondary reforming catalyst.
  • raw synthesis gas containing hydrogen, nitrogen, carbon monoxide and carbon dioxide formed during reaction of the feedstock in the above steam reforming reactions and nitrogen introduced into the gas through addition of air in the secondary reforming step.
  • Water gas shift and/or carbon dioxide removal steps of the synthesis gas stream are required depending of the desired ratio of methanol product to ammonia product , thus involving the re- lease of CO2 to the atmosphere and the investment in highly expensive and complicated units for conducting the shift conversion and carbon dioxide removal.
  • the present invention is based on a combination of primary and secondary steam reforming using oxygen from the electrolysis of water in the partial oxidation of hydrocar- bon feed stock in the secondary steam reforming process.
  • Hydrogen from the electrolysis is used to adjust the hydrogen/nitrogen molar ratio in the effluent gas from the methanol synthesis to provide an ammonia synthesis gas approximately to the stoichiometric ratio required for the production of ammonia, as well as additional synthesis gas production.
  • this invention is a process for the co-production of methanol and ammonia comprising the steps of
  • step (c) primary steam reforming the hydrocarbon feed stock provided in step (a) to a primary steam reformed gas
  • step (d) providing process air for use in a secondary reforming step by enriching atmos- pheric air with the separate oxygen stream from step (b);
  • step (e) secondary reforming the primary steam reformed gas from step (c) with the oxygen enriched air to a process gas stream comprising hydrogen, nitrogen, carbon oxides;
  • step (f) introducing at least part of the separate hydrogen stream from step (b) into the process gas stream obtained in step (e) or optionally into the process gas stream after a shift and/or carbon dioxide removal step;
  • step (h) purifying the gas effluent from step (g) and obtaining an ammonia synthesis gas containing hydrogen and nitrogen;
  • the amount of hydrogen in the process gas is increased by subjecting at least a part of the process gas stream obtained in step (e) to one or more water gas shift reactions, wherein carbon monoxide is reacted to carbon dioxide and hydrogen according the reaction: CO + H 2 0 ⁇ C0 2 + H 2
  • the process gas for the synthesis methanol is a gas containing the highest pos- sible molar ratio of CO/CO2.
  • At least a part of the carbon dioxide is removed from the process gas stream obtained in step (e) or the water gas shifted process gas stream.
  • Removal of carbon dioxide can be performed by a physical or chemical method known in the art.
  • the methanol synthesis stage is preferably conducted by conventional means by pass- ing the process gas at high pressure and temperatures, such as 60-150 bars and 150- 300°C through at least one methanol reactor containing at least one fixed bed of methanol catalyst.
  • a particularly preferred methanol reactor is a fixed bed reactor cooled by a suitable cooling agent such as boiling water, e.g. boiling water reactor (BWR).
  • BWR boiling water reactor
  • the process gas is compressed by means a compressor arranged in front of the at least one methanol reactor.
  • the invention enables the operation of the methanol and ammonia synthesis section at similar operating pressures, for instance 130 bars, which implies that the process gas needs only be compressed to synthesis pressure upstream the methanol synthesis step and no further compression is necessary after the methanol synthesis.
  • the hydrogen gas stream from the water electrolysis is introduced into the suction section of a process gas compressor in front of a methanol reactor in an amount to provide a molar ratio of the hydrogen to the nitrogen of 2.7-3.3 in the gaseous effluent from the methanol synthesis.
  • the gaseous effluent Prior to the gaseous effluent is passed into the ammonia synthesis loop, the gaseous effluent is preferably purified by removing remaining amounts of carbon monoxide and carbon dioxide, preferably by methanation according to the reactions: CO + 3H 2 ⁇ CH 4 + H 2 0; and
  • the purifying step can also be based on cryogenic methods, like the so-called coldbox process, which also can be used for adjustment of the N2/H2 molar ratio by removing excess of N2.
  • the advantages of the process according to the invention are essentially less con- sumption of hydrocarbon feed stock (natural gas) and process air and less emission of C02 in flue gas from the firing of the primary steam reformer at same production rate of methanol and higher production rate of ammonia compared with the conventional process without electrolysis as summarized in the Comparison Table below.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Electrochemistry (AREA)
  • Metallurgy (AREA)
  • Analytical Chemistry (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Hydrogen, Water And Hydrids (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)

Abstract

A process for the combined preparation of methanol and ammonia based on primary steam reforming a hydrocarbon feed stock and adiabatic secondary reforming with oxygen enriched air from electrolysis of water.

Description

Title: Process for the co-production of methanol and ammonia
The present invention is directed to the co-production of methanol and ammonia. More particular, the invention is based on electrolysis of water and steam reforming of a gas- eous hydrocarbon feed stock in the preparation of a carbon oxide, hydrogen and nitrogen containing synthesis gas, which in a first process stage is subjected to methanol synthesis and in a second process stage to ammonia synthesis.
In the conventional methanol process, synthesis gas is typically prepared in so-called two step reforming process. In the two-step reforming process, a desulfurized hydrocarbon feed stock, usually natural gas, is primary reformed in a fired primary steam methane reformer (SMR) and subsequently in an adiabatic secondary steam reformer by partial oxidation of hydrogen and hydrocarbons and adiabatic steam reforming of residual amounts of hydrocarbons from the partial oxidation step. The adiabatic second- ary reformer is operated with essentially pure oxygen for use in the partial oxidation step. The essentially pure oxygen is typically supplied from an Air Separation Unit (ASU).
Alternatively, to the 2-step reforming, stand-alone SMR or stand-alone autothermal re- forming can be used to prepare the synthesis gas.
Regardless of whether stand-alone SMR, 2-step reforming, or stand-alone ATR is used, the product gas will comprise hydrogen, carbon monoxide, and carbon dioxide as well as other components normally including methane and steam.
Ammonia synthesis gas is conventionally prepared by subjecting hydrocarbon feed of natural gas or higher hydrocarbons to endothermic steam reforming reactions in a fired tubular steam reformer by contact with a steam reforming catalyst. The primary reformed gas is then fed into an adiabatic secondary reformer, wherein part of hydrogen and residual amounts of hydrocarbons in the primary reformed gas are partial oxidized with oxygen enriched process air in presence of a secondary reforming catalyst. From the secondary reformer, raw synthesis gas containing hydrogen, nitrogen, carbon monoxide and carbon dioxide formed during reaction of the feedstock in the above steam reforming reactions and nitrogen introduced into the gas through addition of air in the secondary reforming step.
Recently, a combination of electrolysis of water for production of hydrogen and air separation for the production of nitrogen has been envisaged for the preparation of ammo- nia synthesis gas. The thus produced hydrogen and nitrogen are combined in stoichiometric ratios to form synthesis gas for ammonia production. The problem with the combination of electrolysis and air separation is, however, that oxygen is produced as byproduct in both electrolysis and air separation, which has no use in the ammonia synthesis, and can be considered as energy losses.
Current processes for co-production of methanol and ammonia involve generally parallel processes in which a common reforming section is used to generate a synthesis gas which is split in separate parallel streams, one of which is used for methanol synthesis and the other for ammonia synthesis. The co-production of methanol and ammonia can also be conducted sequentially or in series, where the synthesis gas produced in the reforming section is first converted to methanol and the unreacted gas containing carbon oxides and hydrogen is subsequently used for ammonia synthesis. Water gas shift and/or carbon dioxide removal steps of the synthesis gas stream are required depending of the desired ratio of methanol product to ammonia product , thus involving the re- lease of CO2 to the atmosphere and the investment in highly expensive and complicated units for conducting the shift conversion and carbon dioxide removal.
The present invention is based on a combination of primary and secondary steam reforming using oxygen from the electrolysis of water in the partial oxidation of hydrocar- bon feed stock in the secondary steam reforming process. Hydrogen from the electrolysis is used to adjust the hydrogen/nitrogen molar ratio in the effluent gas from the methanol synthesis to provide an ammonia synthesis gas approximately to the stoichiometric ratio required for the production of ammonia, as well as additional synthesis gas production.
Compared to prior art methods using electrolysis of water for hydrogen production and air separation for nitrogen production, the oxygen product from electrolysis of water is advantageously used for partial oxidation in the secondary reformer so that the costly and energy intensive ASU is avoided in the method according to the invention. Thus, this invention is a process for the co-production of methanol and ammonia comprising the steps of
(a) providing a hydrocarbon feed stock;
(b) preparing a separate hydrogen stream and a separate oxygen stream by electrolysis of water;
(c) primary steam reforming the hydrocarbon feed stock provided in step (a) to a primary steam reformed gas;
(d) providing process air for use in a secondary reforming step by enriching atmos- pheric air with the separate oxygen stream from step (b);
(e) secondary reforming the primary steam reformed gas from step (c) with the oxygen enriched air to a process gas stream comprising hydrogen, nitrogen, carbon oxides;
(f) introducing at least part of the separate hydrogen stream from step (b) into the process gas stream obtained in step (e) or optionally into the process gas stream after a shift and/or carbon dioxide removal step;
(g) catalytically converting the carbon oxides and a part of the hydrogen contained in the process gas stream in a once-through methanol synthesis stage and withdrawing an effluent containing methanol and a gas effluent containing un-converted carbon oxides, hydrogen and nitrogen;
(h) purifying the gas effluent from step (g) and obtaining an ammonia synthesis gas containing hydrogen and nitrogen; and
(i) catalytically converting the nitrogen and the hydrogen of the ammonia synthesis gas in an ammonia synthesis stage and withdrawing an effluent containing ammonia. The methanol synthesis in the absence of carbon dioxide is governed by the reaction CO + 2 H2 ^ CH3OH. In the presence of carbon dioxide, methanol is otherwise also generated according to the reaction CO2 + 3 H2 ^ CH3OH + H2O. As apparent from the latter methanol synthesis reaction a lower molar ratio of CO/CO2 in the synthesis gas for the methanol synthesis requires a larger amount of hydrogen.
Thus, in an embodiment of the invention the amount of hydrogen in the process gas is increased by subjecting at least a part of the process gas stream obtained in step (e) to one or more water gas shift reactions, wherein carbon monoxide is reacted to carbon dioxide and hydrogen according the reaction: CO + H20≠ C02 + H2
Ideally, the process gas for the synthesis methanol is a gas containing the highest pos- sible molar ratio of CO/CO2.
Thus, in further an embodiment of the invention at least a part of the carbon dioxide is removed from the process gas stream obtained in step (e) or the water gas shifted process gas stream.
Removal of carbon dioxide can be performed by a physical or chemical method known in the art.
The methanol synthesis stage is preferably conducted by conventional means by pass- ing the process gas at high pressure and temperatures, such as 60-150 bars and 150- 300°C through at least one methanol reactor containing at least one fixed bed of methanol catalyst. A particularly preferred methanol reactor is a fixed bed reactor cooled by a suitable cooling agent such as boiling water, e.g. boiling water reactor (BWR). To provide the required methanol synthesis pressure, the process gas is compressed by means a compressor arranged in front of the at least one methanol reactor.
Accordingly, the invention enables the operation of the methanol and ammonia synthesis section at similar operating pressures, for instance 130 bars, which implies that the process gas needs only be compressed to synthesis pressure upstream the methanol synthesis step and no further compression is necessary after the methanol synthesis. The hydrogen gas stream from the water electrolysis is introduced into the suction section of a process gas compressor in front of a methanol reactor in an amount to provide a molar ratio of the hydrogen to the nitrogen of 2.7-3.3 in the gaseous effluent from the methanol synthesis.
Prior to the gaseous effluent is passed into the ammonia synthesis loop, the gaseous effluent is preferably purified by removing remaining amounts of carbon monoxide and carbon dioxide, preferably by methanation according to the reactions: CO + 3H2≠ CH4 + H20; and
C02 + 4H2≠ CH4 + 2 H20 The purifying step can also be based on cryogenic methods, like the so-called coldbox process, which also can be used for adjustment of the N2/H2 molar ratio by removing excess of N2.
The advantages of the process according to the invention are essentially less con- sumption of hydrocarbon feed stock (natural gas) and process air and less emission of C02 in flue gas from the firing of the primary steam reformer at same production rate of methanol and higher production rate of ammonia compared with the conventional process without electrolysis as summarized in the Comparison Table below.
Comparison Table
Figure imgf000006_0001
Efficiency of the electrolysis is 60%

Claims

Claims
1 . Process for the co-production of methanol and ammonia comprising the steps of
(a) providing a hydrocarbon feed stock;
(b) preparing a separate hydrogen stream and a separate oxygen stream by electrolysis of water;
(c) primary steam reforming the hydrocarbon feed stock provided in step (a) to a primary steam reformed gas;
(d) providing process air for use in a secondary reforming step by enriching atmospheric air with the separate oxygen stream from step (b);
(e) secondary reforming the primary steam reformed gas from step (c) with the oxygen enriched air to a process gas stream comprising hydrogen, nitrogen, carbon oxides;
(f) introducing at least part of the separate hydrogen stream from step (b) into the pro- cess gas stream obtained in step (e) or optionally into the process gas stream after a shift and/or carbon dioxide removal step;
(g) catalytically converting the carbon oxides and a part of the hydrogen contained in the process gas stream in a once-through methanol synthesis stage and withdrawing an effluent containing methanol and a gas effluent containing un-converted carbon ox- ides, hydrogen and nitrogen;
(h) purifying the gas effluent from step (g) and obtaining an ammonia synthesis gas containing hydrogen and nitrogen; and
(i) catalytically converting the nitrogen and the hydrogen of the ammonia synthesis gas in an ammonia synthesis stage and withdrawing an effluent containing ammonia.
2. Process of claim 1 , wherein at least a part of the process gas stream from step (e) is subjected one or more water gas shift reactions.
3. Process of claim 1 or 2, wherein at least a part of the process gas stream from step (e) is subjected to carbon dioxide removal.
4. Process of any one of claims 1 to 3, wherein the purifying of the gas effluent in step (h) comprises methanation.
5. Process of any one of claims 1 to 3, wherein the purifying of the gas effluent in step (h) comprises a cryogenic process.
6. Process of any one of claims 1 to 5, wherein the electrolysis of water in step (b) is powered by renewable energy.
PCT/EP2018/069793 2017-07-25 2018-07-20 Process for the co-production of methanol and ammonia WO2019020522A1 (en)

Priority Applications (14)

Application Number Priority Date Filing Date Title
US16/622,463 US11053130B2 (en) 2017-07-25 2018-07-20 Process for the co-production of methanol and ammonia
CA3070745A CA3070745A1 (en) 2017-07-25 2018-07-20 Process for the co-production of methanol and ammonia
KR1020207003908A KR102599470B1 (en) 2017-07-25 2018-07-20 Process for simultaneous production of methanol and ammonia
EP18743790.0A EP3658493B1 (en) 2017-07-25 2018-07-20 Process for the co-production of methanol and ammonia
CN201880045412.3A CN110831893A (en) 2017-07-25 2018-07-20 Combined production of methanol and ammonia
BR112020001511-3A BR112020001511B1 (en) 2017-07-25 2018-07-20 PROCESS FOR THE COPRODUCTION OF METHANOL AND AMMONIA
PL18743790.0T PL3658493T3 (en) 2017-07-25 2018-07-20 Process for the co-production of methanol and ammonia
NZ760487A NZ760487A (en) 2017-07-25 2018-07-20 Process for the co-production of methanol and ammonia
AU2018308863A AU2018308863B2 (en) 2017-07-25 2018-07-20 Process for the co-production of methanol and ammonia
PE2020000124A PE20200652A1 (en) 2017-07-25 2018-07-20 PROCESS FOR THE CO-PRODUCTION OF METHANOL AND AMMONIA
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